US4248911A - Concentrated heavy duty particulate laundry detergent - Google Patents
Concentrated heavy duty particulate laundry detergent Download PDFInfo
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- US4248911A US4248911A US05/746,900 US74690076A US4248911A US 4248911 A US4248911 A US 4248911A US 74690076 A US74690076 A US 74690076A US 4248911 A US4248911 A US 4248911A
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- zeolite
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- detergent
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
- C11D17/065—High-density particulate detergent compositions
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/06—Phosphates, including polyphosphates
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/128—Aluminium silicates, e.g. zeolites
Definitions
- This invention relates to improved free flowing, high bulk density, particulate, heavy duty laundry detergents. More particularly, it relates to such products comprising sodium tripolyphosphate particles, ion exchanging zeolite particles and a normally liquid or pasty nonionic detergent. Also within the invention are methods for the manufacture of such products.
- This invention is directed to a method of making a free-flowing particulate heavy duty laundry detergent having a bulk density of at least about 0.6 gm/cc. and comprising substantially globular sodium tripolyphosphate particles, zeolite particles, and nonionic detergent; wherein said tripolyphosphate particles include 5-15% water and about 10-20% of sodium silicate having an Na 2 O:SiO 2 ratio in the range of about 1:1.6 to about 1:3.0; and wherein said zeolite is a crystalline, amorphous or mixed crystalline and amorphous zeolite wherein the exchange rate and capacity of said zeolite particles is such that when about 375 ppm of said zeolite on an anhydrous basis is placed in water at 45° C.
- said nonionic detergent is selected from the group consisting of fatty alcohol polyethylene oxide condensates wherein the higher fatty alcohol is of about 10 to 18 carbon atoms and the polyethylene oxide is of about 3-15 moles of ethylene oxide per mole of higher fatty alcohol; said method comprising mixing together about 30 to 50% of said tripolyphosphate particles with from about 5-30% of said nonionic detergent, said nonionic detergent being in liquid form so that the detergent is absorbed by and coats the particles, and admixing with said nonionic detergent coated particles from about 30-50% of zeolite particles, which zeolite particles adhere to the detergent on the surfaces of the particles to make them free flowing and to provide a first formed particle; and applying a second coating of nonionic detergent
- Heavy duty powdered laundry detergents based on synthetic organic detergents and builder salts are well known and have been employed extensively as household and commercial detergents for washing soiled clothing and other such items.
- Sodium tripolyphosphate is among the best of such builder salts and nonionic detergents have been employed as supplemental or principal detergents in heavy duty laundry products.
- Phosphate contents of detergent compositions have been limited by law and regulations in view of evidence which has been interpreted to indicate that they contribute to eutrophication of inland waters when discharged into such waters either directly or indirectly and accordingly, substitute builders have been sought.
- the zeolites particularly, the molecular sieve zeolites of types A, X and Y, all of which are sodium aluminosilicates (hydrated or anhydrous) and which are of high calcium ion exchanging capacities.
- a free flowing, particulate, heavy duty laundry detergent of bulk density of at least 0.6 g./cc. and particle sizes in the range of 4 to 140 mesh comprises sodium tripolyphosphate particles, ion exchanging zeolite particles and normally liquid or pasty nonionic detergent, with the tripolyphosphate particles being of sizes in the 8 to 140 mesh range, U.S. Standard Sieve Series, the zeolite being of ultimate particle diameters in the range of 0.01 to 20 microns and the nonionic detergent being in the interior and at the surfaces of the tripolyphosphate particles and adhering the zeolite particles to the tripolyphosphate particles.
- Also within the invention is a method of making such products by pre-mixing the sodium tripolyphosphate particles and smaller zeolite particles and then admixing with such mixture a nonionic detergent in liquid form so as to cause the detergent to penetrate the sodium tripolyphosphate particles and adhere the zeolite to the surfaces of such particles.
- the products made are excellent concentrated particulate detergents of high bulk density, making it possible to utilize small volumes thereof, e.g., 50-125 cc., for an average wash in an automatic washing machine (which has a tub volume of about 65 liters and washes a charge of about 4 kg. of soiled garments, etc.).
- an automatic washing machine which has a tub volume of about 65 liters and washes a charge of about 4 kg. of soiled garments, etc.
- smaller packages may be employed for similar effective quantities of detergent compositions and shelf space may be conserved in the supermarket and in the home.
- the zeolites which may be employed in practicing the present invention include the crystalline, amorphous and mixed crystalline-amorphous zeolites of both natural and synthetic origins which are of satisfactorily quick and sufficiently effective activities in counteracting hardness ions, such as calcium ions, in wash waters.
- hardness ions such as calcium ions
- such materials are capable of reacting sufficiently rapidly with hardness cations, such as calcium, magnesium, iron and the like or any one of them, to soften wash water before adverse reactions of such hardness ions with other components of the synthetic organic detergent composition occur.
- the zeolites employed may be characterized as having a high exchange capacity for calcium ion, which is normally from about 200 milligram equivalents of calcium carbonate hardness per gram of the aluminosilicate to 400 or more of such milligram equivalents, and a hardness depletion rate residual hardness of 0.02 to 0.05 mg. CaCO 3 /liter in one minute, on an anhydrous zeolite basis.
- the exchange capacity will be between 250 and 350 mg. eq./g. and the residual hardness will be of 0.02 to 0.03 mg./l. and most preferably less than 0.01 mg./l.
- x is 1, y is from 0.8 to 1.2, preferably about 1, z is from 1.5 to 3.5, preferably 2 to 3 or about 2 and w is from 0 to 9, preferably 2.5 to 6.
- the water soluble crystalline aluminosilicates used are often characterized by having a network of substantially uniformly sized pores in the range of about 3 to 10 Angstroms, often being about 4 A (normal), such size being uniquely determined by the unit structure of the zeolite crystal.
- zeolites containing two or more such networks of different pore sizes can also be satisfactorily employed, as can mixtures of such crystalline materials with each other and with amorphous materials, etc.
- the zeolite should be a univalent cation-exchanging zeolite, i.e., it should be an aluminosilicate of a univalent cation such as sodium, potassium, lithium (when practicable) or other alkali metal, or ammonium.
- a univalent cation such as sodium, potassium, lithium (when practicable) or other alkali metal, or ammonium.
- the univalent cation of the zeolite molecular sieve is an alkali metal cation, especially sodium or potassium and most preferably, is sodium, but various other types are also useful.
- Crystalline types of zeolites utilizable as molecular sieves in the invention include zeolites of the following crystal structure groups: A, X, Y, L, mordenite and erionite, of which types A, X and Y are preferred. Mixtures of such molecular sieve zeolites can also be useful, especially when type A zeolite is present.
- These crystalline types of zeolites are well known in the art and are more particularly described in the text Zeolite Molecular Sieves by Donald W. Breck, published in 1974 by John Wiley & Sons. Typical commercially available zeolites of the aforementioned structural types are listed in Table 9.6 at pages 747-749 of the Breck text, which table is incorporated herein by reference.
- the zeolite used in the invention is synthetic and it is also preferable that it be of type A or similar structure, particularly described at page 133 of the aforementioned text.
- Good results have been obtained when a Type 4A molecular sieve zeolite is employed, wherein the univalent cation of the zeolite is sodium and the pore size of the zeolite is about 4 Angstroms.
- Such zeolite molecular sieves are described in U.S. Pat. No. 2,882,243, which refers to them as Zeolite A.
- Molecular sieve zeolites can be prepared in either a dehydrated or calcined form which contains from about 0 or about 1.5% to about 3% of moisture or in a hydrated or water loaded form which contains additional bound water in an amount from about 4% up to about 36% of the zeolite total weight, depending on the type of zeolite used.
- the water-containing hydrated form of the molecular sieve zeolite (preferably about 15 to 70% hydrated) is preferred in the practice of this invention when such crystalline product is used. The manufacture of such crystals is well known in the art.
- the hydrated zeolite crystals that are formed in the crystallization medium are used without the high temperature dehydration (calcining to 3% or less water content) that is normally practiced in preparing such crystals for use as catalysts, e.g., cracking catalysts.
- the crystalline zeolite in either completely hydrated or partially hydrated form, can be recovered by filtering off the crystals from the crystallization medium and drying them in air at ambient temperature so that their water contents are in the range of about 5 to 30% moisture, preferably about 10 to 25%, such as 17 to 22%.
- the moisture content of the molecular sieve zeolite being employed may be much lower, as was previously described.
- the zeolites used as molecular sieves should usually also be substantially free of adsorbed gases, such as carbon dioxide, since such gas-containing zeolites can produce undesirable foaming when the zeolite-containing detergent is contacted with water; however, sometimes the foaming is tolerated and it may sometimes be desirable.
- gases such as carbon dioxide
- the zeolite should be in a finely divided state with the ultimate particle diameters being up to 20 microns, e.g., 0.005 or 0.01 to 20 microns, preferably being from 0.01 to 15 microns and especially preferably of 0.01 to 7 microns mean particle size, e.g., 3 to 7 or 12 microns, if crystalline, and 0.01 to 0.1 micron, e.g., 0.01 to 0.05 microns, if amorphous.
- the ultimate particle diameters being up to 20 microns, e.g., 0.005 or 0.01 to 20 microns, preferably being from 0.01 to 15 microns and especially preferably of 0.01 to 7 microns mean particle size, e.g., 3 to 7 or 12 microns, if crystalline, and 0.01 to 0.1 micron, e.g., 0.01 to 0.05 microns, if amorphous.
- crystalline synthetic zeolites are more common and better known, amorphous zeolites may be employed instead and are often superior to the crystalline materials in various important properties, as will be described, as may be mixed crystalline-amorphous materials and mixtures of the various types of zeolites described.
- the particle sizes and pore sizes of such materials may be like those previously described but variations from the indicated ranges may be made, as described, providing that the materials function satisfactorily as builders and do not objectionably overwhiten dyed materials with which they are treated in aqueous media.
- a preferred ion exchange zeolite is the amorphous zeolite of Belgian patent No. 835,351 of the formula
- Sodium tripolyphosphate also known as pentasodium tripolyphosphate (Na 5 P 3 O 10 ) will preferably be employed as a spray dried product resulting from the drying of a crutcher mix of aqueous pentasodium tripolyphosphate.
- Such spray dried beads are rounded and often are substantially globular, facilitating flow, and they often contain hollows and openings, helping to make them sorptive.
- other forms of the phosphate made by other processes, may also be employed, with rounded, rather than angular particles being highly preferred for their contribution to free flow of the detergent composition, the spray dried products are much preferred.
- Such products may be obtained by spray drying an aqueous sodium tripolyphosphate suspension-solution (crutcher mix) or a crutcher mix which includes other heat stable components of the detergent composition too, some of which will be mentioned subsequently.
- aqueous sodium tripolyphosphate suspension-solution e.g., sodium tripolyphosphate
- crutcher mix e.g., a crutcher mix which includes other heat stable components of the detergent composition too, some of which will be mentioned subsequently.
- at least 60%, preferably 70% and most preferably, about 75% of the particles herein called sodium tripolyphosphate particles should be of the tripolyphosphate, with the balance normally being water (the tripolyphosphate is often partially hydrated), other builder salts, e.g., sodium silicate, and minor adjuvants, e.g., fluorescent brightener(s), stabilizer(s), colorant(s).
- nonionic detergents include those described at length in McCutcheon's Detergents and Emulsifiers, 1973 Annual and in Surface Active Agents, Vol. II, by Schwartz, Perry and Berch (Interscience Publishers, 1958), the descriptions of which are hereby incorporated by reference.
- Such nonionic detergents are usually pasty or waxy solids at room temperature (20° C.) which are either sufficiently water soluble to dissolve promptly in water or will quickly melt at the temperature of the wash water, as when that temperature is above 40° C.
- the nonionic detergents employed will normally be those which are liquid or pasty at room temperature but preference will be given to normally pasty, semi-solid or solid products because such are less liable to make a tacky product of poor flow properties and susceptibility toward lumping or setting on storage. Also they are less liable to weep and release their "holds" on the zeolites. Still, the useful nonionic detergents will be liquefiable so that they may be sprayed at reasonable temperatures, such as those below 45°, 50° or 60° C.
- Typical useful detergents are the poly-(lower alkenoxy) derivatives that are usually prepared by the condensation of lower (2 or 4 carbon atoms) alkylene oxide, e.g., ethylene oxide, propylene oxide (with enough ethylene oxide to make a water soluble product) with a compound having a hydrophobic hydrocarbon chain and containing one or more active hydrogen atoms, such as higher alkyl phenols, higher fatty acids, higher fatty mercaptans, higher fatty amines and higher fatty polyols and alcohols, e.g., fatty alcohols having 8 to 20 or 10 to 18 carbon atoms in an alkyl chain and alkoxylated with an average of about 3 to 30, preferably 3 to 15 or 6 to 12 lower alkylene oxide units.
- alkylene oxide e.g., ethylene oxide, propylene oxide (with enough ethylene oxide to make a water soluble product)
- a compound having a hydrophobic hydrocarbon chain and containing one or more active hydrogen atoms
- Preferred nonionic surfactants are those represented by the formula RO[C 2 H 4 O) n H, wherein R is the residue of a linear saturated primary alcohol (an alkyl) of 10 or 12 to 18 carbon atoms and n is an integer from 3 or 6 to 15.
- Neodol® 45-11 which is an ethoxylation product (having an average of about 11 ethylene oxide units) of a 14 to 15 carbon atom (average) chain fatty alcohol (made by Shell Chemical Company); Neodol 25-7, a 12 to 15 carbon atom chain fatty alcohol ethoxylated with an average of 7 ethylene oxide units; and Alfonic® 1618-65, which is a 16 to 18 carbon alkanol ethoxylated with an average of 10 to 11 ethylene oxide units (Continental Oil Company). Also useful are the Igepals® of GAF Co., Inc.
- Such materials are usually the polyethoxylated (3 to 30 ethylene oxide units) middle alkyl (6 to 10 carbon atoms) phenols, such as Igepals CA-630, CA-730 and CO-630.
- the Pluronics® (made by BASF-Wyandotte), such as Pluronic F-68 and F-127, which are condensates of ethylene oxide with hydrophobic bases formed by condensing propylene oxide with propylene glycol, usually having molecular weights in the range of 5,000 to 25,000, may also be employed, as may be the various Tweens® (Atlas Chemical Industries), which are polyoxyethylene sorbitan higher fatty acid (12 to 18 carbon atoms) esters, such as those containing 20 to 85 mols of ethylene oxide per mol.
- nonionic detergents described in the texts previously incorporated by reference may also be employed but preferably the proportion of nonionic detergent or surface active agent present, when other than the higher fatty alcohol polyoxyethylene ethanols, will be a minor one, rarely being more than 50% and preferably no more than 25% of the total nonionic detergent content.
- higher as in higher alkyl, higher fatty, etc., means from 8 to 20, preferably from 10 or 12 to 18.
- various other builders may also be present, such as alkali metal carbonates, bicarbonates, borates, silicates and other phosphates but with the exception of the silicates, which are especially useful as anti-corrosion additives, in addition to having sequestering powers (especially for magnesium ions) it is generally preferred to omit other builders although in some cases carbonates may also be desired components.
- the sum of such builders will be a minor one in the composition and in the spray dried phosphate beads, in which they will usually be present. Normally the content of such builder salts will total no more than 25% of the total of such builder salt plus tripolyphosphate in the product.
- the proportion thereof will be 4 to 10% in the final product, e.g., 6%, and 10 to 30% in the tripolyphosphate granules, more preferably 10 to 20%.
- the silicate should be of Na 2 O:SiO 2 ratio in the range of 1:1.6 to 1:3.0, preferably 1:2.0 to 1:2.7 and most preferably about 1:2.4.
- nonionic synthetic organic detergents are important components of the present products they may be partially replaced or supplemented by anionic organic detergents and in some cases by amphoteric organic detergents, too.
- the nonionic content will be the major proportion of the detergent present and normally the proportion of anionic detergent and/or amphoteric detergent in the final product will be less than 10%.
- the anionic detergents will be sufficiently heat stable to be capable of being spray dried with the polyphosphate but they may also be suitably combined with the nonionic detergent being sprayed onto the surfaces of the mixture of zeolite and phosphate or may sometimes be mixed with the polyphosphate and zeolite before addition of the nonionic.
- anionic detergents that are useful are the sulfates, sulfonates and phosphonates of lipophilic moieties, especially those containing higher carbon atom chains, such as those of 8 to 20 or 10 to 18 carbon atoms. Included among such compounds are the linear higher alkylbenzene sulfonates, olefin sulfonates, paraffin sulfonates, fatty acid soaps, higher fatty alcohol sulfates, higher fatty acid monoglyceride sulfates, sulfated condensation products of ethylene oxide (3 to 30 mols per mol) and higher fatty alcohol, higher fatty acid esters of isethionic acid and other known anionic detergents, such as also are mentioned in the texts previously incorporated herein by reference.
- anionic detergents include sodium linear tridecyl benzene sulfonate, sodium cocomonoglyceride sulfate, sodium lauryl sulfate and sodium paraffin and olefin sulfonates, each of an average of about 16 carbon atoms.
- amphoteric compounds such as the sodium salt of Miranol® C 2 M and Deriphat® 151 may be employed in the present detergents in replacement of all or part, e.g., up to 50%, of the anionic detergent, usually no amphoteric detergent will be present.
- the amphoterics may be spray dried or otherwise co-formed with the tripolyphosphates or may be dispersed in the liquid nonionic detergent or mixed with other powders during the making of the present products.
- compositions such as bleaches, e.g., sodium perborate; colorants, e.g., pigments, dyes; fluorescent brighteners, e.g., stilbene brighteners; foam stabilizers, e.g., alkanolamides, such as lauric myristic diethanolamide; enzymes, e.g., proteases; skin protecting and conditioning agents, such as water soluble proteins of low molecular weight, obtained by hydrolysis of proteinaceous materials, such as animal hair, hides, gelatin, collagen; foam destroyers, e.g., silicones; bactericides, e.g., hexachlorophene; and perfumes.
- bleaches e.g., sodium perborate
- colorants e.g., pigments, dyes
- fluorescent brighteners e.g., stilbene brighteners
- foam stabilizers e.g., alkanolamides, such as lauric myristic diethanolamide
- enzymes
- the proportions of tripolyphosphate particles, zeolite and nonionic detergent in the product should be chosen to obtain the desired free-flowing product of satisfactory high bulk density, when made by the method of this invention. Such proportions are 30 to 50% of tripolyphosphate particles, 30 to 50% of zeolite and 5 to 30% of nonionic detergent, with preferred ranges being 35 to 45%, 35 to 45% and 10 to 30%, respectively.
- the bulk density of the product will be at least 0.6 g./cc., preferably being 0.75 to 0.95 g/cc. and most preferably being about 0.8 to 0.9 g./cc.
- the particle sizes of the product will be in the 4 to 140 mesh range, preferably being 6 or 8 to 100 mesh.
- the particle sizes of the tripolyphosphate particles will be in the range of 8 to 140 mesh, preferably being 8 to 100 mesh and the zeolite powder, although much smaller in ultimate particle size, will usually be in the range of 100 to 400 mesh, preferably being 140 to 325 mesh.
- the tripolyphosphate powder charged to the crutcher may be of any suitable particle size and the crutcher mix will normally have a moisture content of 30 to 80%, preferably 40 to 70%.
- Spray drying may be in normal spray drying towers, such as countercurrent towers with the spray pressure and nozzle size being adjusted to produce the desired bead structure (spherical), size and moisture content, which will usually be from 2 to 20% therein.
- the bulk density of the polyphosphate beads employed will usually be in the range of 0.4 to 0.8 g./cc. and that of the zeolite powder utilized will be in the same general range.
- the tripolyphosphate particles will normally contain at least 60% of sodium tripolyphosphate, preferably at least 70% thereof and more preferably from 70 to 85% thereof, when there are present other adjuvants, such as 10 to 20% of sodium silicate and from 0.1 to 5% of fluorescent brightener, with 5 to 15% of water, too.
- the free flowing, particulate, high bulk density, heavy duty laundry detergents of this invention are easily made by mixing together the described sodium tripolyphosphate particles and zeolite particles and then admixing with such mixture a nonionic detergent in liquid form.
- the detergent penetrates the sodium tripolyphosphate particles and adheres the zeolite to the surfaces thereof.
- the tripolyphosphate particles are spray dried particles containing at least 60% of sodium tripolyphosphates before addition of the nonionic detergent thereto.
- the nonionic detergent is normally liquid or pasty, preferably pasty or semi-solid, and is sprayed as a liquid onto moving surfaces of the mixture of tripolyphosphate particles and zeolite, such liquid usually being at a temperature over 25° C. and preferably at least 40° C.
- the proportions of materials utilized are such that the product made will be of a desired, previously described composition.
- the initial mixing of sodium tripolyphosphate particles and zeolite is normally effected at room temperature (20° to 25° C.) but the temperature may vary over the range of 10° to 40° C. Such mixing may take as little as 30 seconds or may be effected over a period as long as ten minutes but normally it is preferred to utilize a shorter time, e.g., 1-2 minutes.
- the higher fatty alcohol-polyethylene oxide condensation product is heated to an elevated temperature at which it is liquid and is sprayed onto the moving surfaces of the mixture of tripolyphosphate particles and zeolite.
- the mixing and the spraying of the nonionic detergent onto the moving particles are effected in a rotating tube or drum inclined at a slight angle, e.g., 5° to 15°.
- Rotational speed may be any that is suitable, e.g., 10 to 50 r.p.m.
- Such spraying is usually effected over a period of about 1 to 5 minutes and mixing may be continued afterward for a period of 0 to 10 minutes, preferably 1 to 5 minutes.
- the spraying of the nonionic detergent will normally be such as to produce droplets of particle sizes in the 40 to 100 micron diameter range but other suitable spray sizes may be employed and in some cases the nonionic may be blended with the mixed powders after being dropped or poured onto the moving surfaces thereof.
- a higher speed and higher energy mixer such as one of the Lodige, twin shell or similar type to aid in breaking up any lumps caused by the addition of the larger droplets or streams of nonionic detergent.
- sorptive tripolyphosphate made by methods other than spray drying may also be utilized but it is highly desirable for particles thereof to be rounded rather than angular.
- the product which may have a moisture content of 2 to 20%, preferably 4 to 10%, is ready for packaging.
- various adjuvants can be incorporated in the product by inclusion with suitable components or may be added thereto in suitable processing steps.
- the total adjuvant content, exclusing water, will rarely exceed 20% of the product other than the mentioned tripolyphosphate, zeolite and nonionic detergent and will normally be less than 10% of the product.
- a perborate bleach is utilized the percentage may be increased to an effective bleaching amount, which can be as high as 30% of the product.
- the perborate may be comixed with the zeolite and the tripolyphoshate or may be post-added to such pre-mix or to the nonionic-treated mixture.
- Colorants, perfumes and other adjuvants may be admixed with the various components and mixtures during manufacture or after completion thereof.
- the products of this invention have significant advantages over other low phosphate (8.7% phosphorus and under) heavy duty detergents. They wash well, due to the presence of the tripolyphosphate and the zeolite builders with the comparatively large amount of nonionic detergent. They flow freely and don't cake because the coating of zeolite on the surface of the tripolyphosphate particles prevents any nonionic on the surface thereof from causing tackiness, poor flow properties and caking.
- the nonionic detergent on the surfaces of the tripolyphosphate particles constitutes only a small part, e.g., 10%, of the nonionic detergent in the product because the porous tripolyphosphate particles allow penetration of the nonionic to the interiors thereof and thereby insulate it from contact with the surfaces of the other particles. Also, the rounded particles resulting help minimize contact areas and possible agglomeration. When amorphous zeolites are employed there is an improvement in non-deposition properties compared to when crystalline zeolites are utilized. Because of the presence of the nonionic detergent adjacent to the zeolite particles suspension thereof is promoted and deposition on or entrapment in the laundry is minimized.
- the products made are stable, non-caking under normal storage, resistant to bleeding of the nonionic, non-dusting, non-settling, free flowing, attractive and effective. Furthermore, because of their high bulk densities they are more convenient to pack, store and use. Additionally, they are readily made by a process which is energy conserving because only a fraction of the product is spray dried. Still further, because the nonionic is post-added little air pollution is caused by the manufacturing method, compared to that resulting when products containing substantial proportions of nonionic detergent are spray dried.
- the proportions of nonionic detergent and zeolite employed in each recoating will be within the proportions of the ranges of percentages of these materials in the original detergent composition, the final product will be within the percentage ranges of components given and the sum of the percentages of nonionic detergent and zeolite particles utilized in recoating will be less than halves of the percentages of such materials present in the product to be recoated and preferably will be less than 30% thereof.
- the recoating operations may be conducted in the same tumbling drums as previously described and under the same mixing conditions previously mentioned for the applications of the nonionic and zeolite.
- the pentasodium tripolyphoshate granules are made by spray drying an aqueous slurry of the described materials with a moisture content of 40% in a countercurrent spray drying tower to produce beads of the formula given, having particle sizes in the 8 to 140 mesh, U.S. Standard Sieve Series, range.
- the spray dried particles at a temperature of about 25° C., are mixed over a period of one minute in a twin-shell blender with the formula amount of the zeolite powder, which is of a particle size in the 170 to 270 mesh range.
- the intermediate product is transferred to an inclined rotating drum, into which there is sprayed the nonionic detergent at a temperature of 45° C., at which temperature it is in liquid form.
- the droplets sprayed are of particle sizes largely in the range of 40 to 100 microns in diameter and they are impinged onto the moving surfaces of the mixture of zeolite and tripolyphoshpate as the drum rotates at 40 r.p.m. After three minutes all the nonionic detergent has been sprayed onto the product and after another three minutes it has been sufficiently sorbed and has adhered the smaller zeolite particles to the surfaces of the tripolyphosphate particles. Some of the zeolite particles also penetrate into some of the pores of the tripolyphosphate particles, as does some of the nonionic detergent, with approximately 5 to 20%, e.g., 10% of the nonionic remaining at the surfaces of the particles. A small proportion of the zeolite powder becomes agglomerated during spraying and mixing because of the comparatively large proportion thereof in the present formula but the particle sizes of the agglomerates approximate those of the other particles and do not contribute to tackiness.
- the particulate laundry detergent made is of a bulk density of about 0.8 g./cc., at least twice that normally obtained for commercial heavy duty laundry detergent compositions. Because or at least partially because of its greater bulk density it is more convenient to use and store, is stable on storage, is of excellent flow properties, is non-tacky and non-caking and does not dust objectionably when poured.
- the phosphorus content thereof is under 8.7% and therefore the product is in accordance with government regulations in many areas.
- the resulting product is also an excellent free flowing detergent but the beads are more friable, although acceptable, and without the presence of the silicate detergent they are also somewhat more corrosive to aluminum parts.
- the product is a useful, non-tacky, free flowing detergent of a high bulk density of about 0.7 to 0.8 g./cc.
- the spray dried pentasodium tripolyphosphate beads, the silicate particles (of particle sizes in the 100 to 200 mesh range) and the zeolite powder are mixed together and the nonionic detergent is admixed with them according to the primary method of Example 1.
- the product resulting is a good heavy duty detergent which is free flowing and of high bulk density (0.7 to 0.8 g./cc.).
- the hydrous sodium silicate of smaller particle size in the spray dried tripolyphosphate particles the flowability is not as good as that of the comparable product of Example 1.
- Similar results are obtained when instead of the spray dried pentasodium tripolyphosphate there are employed tetrasodium pyrophosphate particles of similar particle size.
- Neodol 25-3S sodium polyethoxy higher fatty alcohol sulfate [C 12-15 alcohol and 3 mols of ethylene oxide per mol]
- 60% active ingredient, 25% H 2 O and 15% C 2 H 5 OH, mfd. by Shell Chemical Company being heated and mixed with the Neodol 25-7 and sprayed onto the tumbling beads, a good free flowing high bulk density product results.
- the phosphate (or other suitable water soluble builder salt) and all other water soluble builder salts present are coated, internally and externally, with the Neodol 25-7 nonionic detergent and the resulting particles, resembling wet sand particles, in that they do not cohere strongly, and have a waxy, greasy appearance, are coated with the zeolite, with mixing times for the various mixings and coatings being about five minutes each, satisfactory high density flowable detergent products result.
- the two coating operations usually take more time and are somewhat more difficult to control than the previously described method.
- the products made are of desirable bulk densities, usually being about 0.8 g./cc.
- Example 3 describes a further modification and improvement in the products and methods of this invention, wherein additional quantities of nonionic detergent are incorporated in the product by utilization of sequential coating or recoating techniques.
- the liquid nonionic detergent is applied in sufficient quantity so that it penetrates into the interiors of the nucleus or base particles, with such an excess present that it wets the surfaces of the particles so as to cause the zeolite powder to adhere to such surfaces.
- the excess liquid causes or promotes the production of an agglomerate or paste and a satisfactorily free flowing product is not obtainable.
- the particle size may be increased desirably.
- the additional coatings help to protect the components of the product (base beads, other builders and detergents, fluorescent brighteners, enzymes, and other adjuvants, from the air and moisture in it.
- Example 1-3 The procedures of Examples 1-3 are followed but in each case, based on 100 parts of product resulting from the practice of the methods of those examples, an additional five parts of the nonionic detergent are sprayed onto the product and an additional ten parts of zeolite are then mixed in with the product to be adhered to the nonionic coating thereon (using the spraying and mixing procedures described in Examples 1-3).
- the particle size increases about 5% (diameter) but the product is still of about the same bulk density as was previously obtained and still is free flowing and non-lumping.
- an additional five parts of the nonionic detergent are sprayed onto the two-stage product and an additional ten parts of the zeolite are dusted onto this, with similar desirable results (using the same spraying and mixing methods).
- the tripolyphosphate or other base particle will usually not be re-applied but this may be done when advantageous. Normally as many as six coating operations may be employed but it is preferred that this be limited to three such operations, as in the "further experiment" described herein. Also, it is preferred that the totals of nonionic detergent and zeolite in coating operations subsequent to the first operation should be limited to the amounts employed in the first operation and preferably to halves of such amounts, with proportions of the nonionic and zeolite being within the proportions of the previously mentioned percentage ranges.
- Examples 1-4 The procedures of Examples 1-4 are repeated with the tripolyphosphate being replaced by tetrasodium pyrophosphate and by an equal mixture of the pyrophosphate and the tripolyphosphate, types X and Y crystalline zeolites of similar particle sizes and amorphous zeolites being substituted for the type 4A zeolite and Neodols 23-6.5 and 45-11 and Alfonics 1618-65 and 1412-60 being substituted for the Neodol 25-7, and comparable high bulk density, free flowing detergent compositions are made.
- the only changes in manufacturing techniques are in maintaining the temperature of the nonionic detergent sufficiently high to ensure that it is in the liquid state when it is sprayed onto the surfaces of the base particles.
- proportions of the various components are modified ⁇ 10% and ⁇ 30%, while being kept within the ranges of percentages and proportions previously mentioned. Care is taken that the proportion of nonionic detergent employed is such as to provide an unabsorbed portion on the surface of the base beads in the form of an adhering coating so as to hold the zeolite particles.
- the nonionic detergent is normally solid the temperature of the detergent at the time of application of the zeolite or of the zeolite-builder salt mixture is maintained high enough so that the zeolite particles will adhere to it and the base particles.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Priority Applications (21)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US05/746,900 US4248911A (en) | 1976-12-02 | 1976-12-02 | Concentrated heavy duty particulate laundry detergent |
ZA00776947A ZA776947B (en) | 1976-12-02 | 1977-11-21 | Concentrated heavy duty particulate laundry detergent |
SE7713166A SE435729B (sv) | 1976-12-02 | 1977-11-22 | Fririnnande, partikelformig, stark eller hogverkande tvettdetergent |
NZ185756A NZ185756A (en) | 1976-12-02 | 1977-11-23 | Particulate heavy duty laundry detergent coated tripolyphosphate particles |
AU30953/77A AU521529B2 (en) | 1976-12-02 | 1977-11-24 | Laundry detergent |
DE19772753026 DE2753026A1 (de) | 1976-12-02 | 1977-11-28 | Konzentriertes koerniges wasch- und reinigungsmittel fuer grob-, weiss- und buntwaesche |
MX77101083U MX5354E (es) | 1976-12-02 | 1977-11-28 | Mejoras a composicion detergente de lavanderia,particulada,de trabajo pesado y concentrada y metodo para fabricarla |
FR7735914A FR2372892A1 (fr) | 1976-12-02 | 1977-11-29 | Composition detergente concentree en particules pour le lavage du linge |
PT67335A PT67335B (en) | 1976-12-02 | 1977-11-29 | Process for the preparation of a laundry detergent |
CA292,113A CA1096740A (en) | 1976-12-02 | 1977-11-30 | Concentrated heavy duty particulate laundry detergent |
AT0859377A AT374820B (de) | 1976-12-02 | 1977-12-01 | Frei fliessfaehiges, koerniges wasch- und reinigungsmittel fuer grob-, weiss- und buntwaesche |
ES464644A ES464644A1 (es) | 1976-12-02 | 1977-12-01 | Un metodo de fabricar un detergente. |
IT52023/77A IT1092161B (it) | 1976-12-02 | 1977-12-01 | Detersivo concentrato per bucato grosso in polvere fluida e raltivo procedimento di produzione |
GB50121/77A GB1591517A (en) | 1976-12-02 | 1977-12-01 | Detergent compositions |
NL7713386A NL7713386A (nl) | 1976-12-02 | 1977-12-02 | Uit afzonderlijke kleine deeltjes bestaande, vrij vloeiende sterke wasgoeddetergent alsmede werkwijze voor het bereiden daarvan. |
PH20507A PH16878A (en) | 1976-12-02 | 1977-12-02 | Concentrated heavy duty particulate laundry detergent |
CH1477677A CH633581A5 (de) | 1976-12-02 | 1977-12-02 | Frei fliessfaehiges, koerniges, hochleistungsfaehiges wasch- und reinigungsmittel fuer grob-, weiss- und buntwaesche. |
BE183111A BE861432A (fr) | 1976-12-02 | 1977-12-02 | Compositions detergents concentree en particules pour le lavage du linge |
DK537077A DK152588C (da) | 1976-12-02 | 1977-12-02 | Fritstroemmende, partikelformet, kraftigt virkende toejvaskemiddel |
US06/183,022 US4411809A (en) | 1976-12-02 | 1980-09-02 | Concentrated heavy duty particulate laundry detergent |
MY71/83A MY8300071A (en) | 1976-12-02 | 1983-12-30 | Detergent compositions |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US05/746,900 US4248911A (en) | 1976-12-02 | 1976-12-02 | Concentrated heavy duty particulate laundry detergent |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US06/183,022 Division US4411809A (en) | 1976-12-02 | 1980-09-02 | Concentrated heavy duty particulate laundry detergent |
Publications (1)
Publication Number | Publication Date |
---|---|
US4248911A true US4248911A (en) | 1981-02-03 |
Family
ID=25002837
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US05/746,900 Expired - Lifetime US4248911A (en) | 1976-12-02 | 1976-12-02 | Concentrated heavy duty particulate laundry detergent |
Country Status (19)
Country | Link |
---|---|
US (1) | US4248911A (de) |
AT (1) | AT374820B (de) |
AU (1) | AU521529B2 (de) |
BE (1) | BE861432A (de) |
CA (1) | CA1096740A (de) |
CH (1) | CH633581A5 (de) |
DE (1) | DE2753026A1 (de) |
DK (1) | DK152588C (de) |
ES (1) | ES464644A1 (de) |
FR (1) | FR2372892A1 (de) |
GB (1) | GB1591517A (de) |
IT (1) | IT1092161B (de) |
MY (1) | MY8300071A (de) |
NL (1) | NL7713386A (de) |
NZ (1) | NZ185756A (de) |
PH (1) | PH16878A (de) |
PT (1) | PT67335B (de) |
SE (1) | SE435729B (de) |
ZA (1) | ZA776947B (de) |
Cited By (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4332692A (en) * | 1979-02-28 | 1982-06-01 | The Procter & Gamble Company | Laundering with a nonionic detergent system at a temperature between the cloud point and the phase coalescence temperatures |
US4386024A (en) * | 1981-03-21 | 1983-05-31 | Hoechst Aktiengesellschaft | Granulate of alkali metal aluminum silicate and pentasodium tripolyphosphate, and process for making it |
US4436644A (en) | 1979-10-31 | 1984-03-13 | Lever Brothers Company | Adjuncts for use in the manufacture of detergent powders |
US4444674A (en) * | 1980-11-06 | 1984-04-24 | The Procter & Gamble Company | Granular bleach activator compositions and detergent compositions containing them |
JPS6169899A (ja) * | 1984-09-14 | 1986-04-10 | 花王株式会社 | 流動性の改良された高密度の粒状洗剤の製法 |
JPS6169900A (ja) * | 1984-09-14 | 1986-04-10 | 花王株式会社 | 流動性の改良された高密度の粒状洗剤の製法 |
JPS6169897A (ja) * | 1984-09-14 | 1986-04-10 | 花王株式会社 | 流動性の改良された高密度の粒状洗剤の製法 |
US4637891A (en) * | 1981-03-20 | 1987-01-20 | Lever Brothers Company | Process for the manufacture of detergent compositions containing sodium aluminosilicate |
US4663194A (en) * | 1976-12-02 | 1987-05-05 | The Colgate-Palmolive Co. | Phosphate-free concentrated particulate heavy duty laundry detergent |
US4666738A (en) * | 1980-09-02 | 1987-05-19 | The Colgate-Palmolive Co. | Method for making a phosphate containing concentrated heavy duty particulate laundry detergent |
US4743394A (en) * | 1984-03-23 | 1988-05-10 | Kaufmann Edward J | Concentrated non-phosphate detergent paste compositions |
EP0405884A1 (de) * | 1989-06-29 | 1991-01-02 | The Procter & Gamble Company | Elektrostatische Beschichtung von Waschmittelgranulat |
US5045238A (en) * | 1989-06-09 | 1991-09-03 | The Procter & Gamble Company | High active detergent particles which are dispersible in cold water |
US5152932A (en) * | 1989-06-09 | 1992-10-06 | The Procter & Gamble Company | Formation of high active detergent granules using a continuous neutralization system |
US5578561A (en) * | 1992-10-12 | 1996-11-26 | Kao Corporation | Nonionic powdery detergent composition |
US5714451A (en) * | 1996-03-15 | 1998-02-03 | Amway Corporation | Powder detergent composition and method of making |
US5714450A (en) * | 1996-03-15 | 1998-02-03 | Amway Corporation | Detergent composition containing discrete whitening agent particles |
US5990068A (en) * | 1996-03-15 | 1999-11-23 | Amway Corporation | Powder detergent composition having improved solubility |
US5998351A (en) * | 1996-03-15 | 1999-12-07 | Amway Corporation | Discrete whitening agent particles method of making, and powder detergent containing same |
US6177397B1 (en) | 1997-03-10 | 2001-01-23 | Amway Corporation | Free-flowing agglomerated nonionic surfactant detergent composition and process for making same |
DE19882934B3 (de) * | 1997-12-30 | 2012-02-23 | Ecolab Inc. | Verbesserte alkalische Zusammensetzung in Form eines festen Blocks |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2822231A1 (de) * | 1978-05-22 | 1979-11-29 | Hoechst Ag | Granulat aus hydratisiertem natriumtripolyphosphat und wasserunloeslichem alumosilicationenaustauschmaterial |
US4231887A (en) * | 1979-06-26 | 1980-11-04 | Union Carbide Corporation | Zeolite agglomerates for detergent formulations |
DE3038413C2 (de) * | 1980-10-10 | 1986-10-09 | Unilever N.V., Rotterdam | Alkalimetalltripolyphosphat/Alkalimetallsilikat-Cogranulate mit verbessertem Ausspülverhalten |
GB8810821D0 (en) * | 1988-05-06 | 1988-06-08 | Unilever Plc | Detergent compositions & process for preparing them |
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US3290158A (en) * | 1963-03-27 | 1966-12-06 | Huber Corp J M | Process of producing free flowing sodium chloride |
US3755180A (en) * | 1972-02-25 | 1973-08-28 | Colgate Palmolive Co | Means to inhibit overglaze damage by automatic dishwashing detergents |
US3838072A (en) * | 1971-03-15 | 1974-09-24 | Colgate Palmolive Co | Manufacture of free flowing particulate detergent containing nonionic surface active compound |
US3868336A (en) * | 1971-03-11 | 1975-02-25 | Lever Brothers Ltd | Process for improving flowability of detergents |
DE2507926A1 (de) * | 1974-02-25 | 1975-08-28 | Henkel & Cie Gmbh | Nichtionische tenside enthaltende schuettfaehige wasch- und reinigungsmittel und verfahren zu deren herstellung |
US3915878A (en) * | 1971-02-09 | 1975-10-28 | Colgate Palmolive Co | Free flowing nonionic surfactants |
DE2535792A1 (de) * | 1974-08-12 | 1976-03-04 | Sifrance | Reinigungs- und waschmittel |
DE2538680A1 (de) * | 1974-09-06 | 1976-03-18 | Colgate Palmolive Co | Freifliessende waschmittelpulver |
US4007124A (en) * | 1975-02-14 | 1977-02-08 | The Procter & Gamble Company | Process for preparing a silicate-pyrophosphate detergent composition |
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NL7006570A (de) * | 1969-05-29 | 1970-12-01 | ||
AT334491B (de) * | 1974-10-03 | 1976-01-25 | Henkel & Cie Gmbh | Schuttfahiges geruststoff-agglomerat fur wasch- und reinigungsmittel und verfahren zu dessen herstellung |
AT375393B (de) * | 1974-10-04 | 1984-07-25 | Henkel Kgaa | Verfahren zum waschen bzw. bleichen von textilien sowie mittel dazu |
-
1976
- 1976-12-02 US US05/746,900 patent/US4248911A/en not_active Expired - Lifetime
-
1977
- 1977-11-21 ZA ZA00776947A patent/ZA776947B/xx unknown
- 1977-11-22 SE SE7713166A patent/SE435729B/sv not_active IP Right Cessation
- 1977-11-23 NZ NZ185756A patent/NZ185756A/xx unknown
- 1977-11-24 AU AU30953/77A patent/AU521529B2/en not_active Expired
- 1977-11-28 DE DE19772753026 patent/DE2753026A1/de active Granted
- 1977-11-29 FR FR7735914A patent/FR2372892A1/fr active Granted
- 1977-11-29 PT PT67335A patent/PT67335B/pt unknown
- 1977-11-30 CA CA292,113A patent/CA1096740A/en not_active Expired
- 1977-12-01 AT AT0859377A patent/AT374820B/de not_active IP Right Cessation
- 1977-12-01 GB GB50121/77A patent/GB1591517A/en not_active Expired
- 1977-12-01 IT IT52023/77A patent/IT1092161B/it active
- 1977-12-01 ES ES464644A patent/ES464644A1/es not_active Expired
- 1977-12-02 DK DK537077A patent/DK152588C/da active
- 1977-12-02 PH PH20507A patent/PH16878A/en unknown
- 1977-12-02 BE BE183111A patent/BE861432A/xx not_active IP Right Cessation
- 1977-12-02 NL NL7713386A patent/NL7713386A/xx not_active Application Discontinuation
- 1977-12-02 CH CH1477677A patent/CH633581A5/de not_active IP Right Cessation
-
1983
- 1983-12-30 MY MY71/83A patent/MY8300071A/xx unknown
Patent Citations (9)
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US3290158A (en) * | 1963-03-27 | 1966-12-06 | Huber Corp J M | Process of producing free flowing sodium chloride |
US3915878A (en) * | 1971-02-09 | 1975-10-28 | Colgate Palmolive Co | Free flowing nonionic surfactants |
US3868336A (en) * | 1971-03-11 | 1975-02-25 | Lever Brothers Ltd | Process for improving flowability of detergents |
US3838072A (en) * | 1971-03-15 | 1974-09-24 | Colgate Palmolive Co | Manufacture of free flowing particulate detergent containing nonionic surface active compound |
US3755180A (en) * | 1972-02-25 | 1973-08-28 | Colgate Palmolive Co | Means to inhibit overglaze damage by automatic dishwashing detergents |
DE2507926A1 (de) * | 1974-02-25 | 1975-08-28 | Henkel & Cie Gmbh | Nichtionische tenside enthaltende schuettfaehige wasch- und reinigungsmittel und verfahren zu deren herstellung |
DE2535792A1 (de) * | 1974-08-12 | 1976-03-04 | Sifrance | Reinigungs- und waschmittel |
DE2538680A1 (de) * | 1974-09-06 | 1976-03-18 | Colgate Palmolive Co | Freifliessende waschmittelpulver |
US4007124A (en) * | 1975-02-14 | 1977-02-08 | The Procter & Gamble Company | Process for preparing a silicate-pyrophosphate detergent composition |
Cited By (26)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4663194A (en) * | 1976-12-02 | 1987-05-05 | The Colgate-Palmolive Co. | Phosphate-free concentrated particulate heavy duty laundry detergent |
US4332692A (en) * | 1979-02-28 | 1982-06-01 | The Procter & Gamble Company | Laundering with a nonionic detergent system at a temperature between the cloud point and the phase coalescence temperatures |
US4436644A (en) | 1979-10-31 | 1984-03-13 | Lever Brothers Company | Adjuncts for use in the manufacture of detergent powders |
US4666738A (en) * | 1980-09-02 | 1987-05-19 | The Colgate-Palmolive Co. | Method for making a phosphate containing concentrated heavy duty particulate laundry detergent |
US4444674A (en) * | 1980-11-06 | 1984-04-24 | The Procter & Gamble Company | Granular bleach activator compositions and detergent compositions containing them |
US4637891A (en) * | 1981-03-20 | 1987-01-20 | Lever Brothers Company | Process for the manufacture of detergent compositions containing sodium aluminosilicate |
US4386024A (en) * | 1981-03-21 | 1983-05-31 | Hoechst Aktiengesellschaft | Granulate of alkali metal aluminum silicate and pentasodium tripolyphosphate, and process for making it |
US4743394A (en) * | 1984-03-23 | 1988-05-10 | Kaufmann Edward J | Concentrated non-phosphate detergent paste compositions |
JPS6169900A (ja) * | 1984-09-14 | 1986-04-10 | 花王株式会社 | 流動性の改良された高密度の粒状洗剤の製法 |
JPS6169897A (ja) * | 1984-09-14 | 1986-04-10 | 花王株式会社 | 流動性の改良された高密度の粒状洗剤の製法 |
JPS6169899A (ja) * | 1984-09-14 | 1986-04-10 | 花王株式会社 | 流動性の改良された高密度の粒状洗剤の製法 |
JPH045080B2 (de) * | 1984-09-14 | 1992-01-30 | ||
US5152932A (en) * | 1989-06-09 | 1992-10-06 | The Procter & Gamble Company | Formation of high active detergent granules using a continuous neutralization system |
US5045238A (en) * | 1989-06-09 | 1991-09-03 | The Procter & Gamble Company | High active detergent particles which are dispersible in cold water |
US5000978A (en) * | 1989-06-29 | 1991-03-19 | The Procter & Gamble Company | Electrostatic coating of detergent granules |
EP0405884A1 (de) * | 1989-06-29 | 1991-01-02 | The Procter & Gamble Company | Elektrostatische Beschichtung von Waschmittelgranulat |
TR25579A (tr) * | 1989-06-29 | 1993-07-01 | Procter & Gamble | DETERJAN GRANüLLERININ ELEKTROSTATIK KAPLANMASI |
US5578561A (en) * | 1992-10-12 | 1996-11-26 | Kao Corporation | Nonionic powdery detergent composition |
US5714451A (en) * | 1996-03-15 | 1998-02-03 | Amway Corporation | Powder detergent composition and method of making |
US5714450A (en) * | 1996-03-15 | 1998-02-03 | Amway Corporation | Detergent composition containing discrete whitening agent particles |
US5990068A (en) * | 1996-03-15 | 1999-11-23 | Amway Corporation | Powder detergent composition having improved solubility |
US5998351A (en) * | 1996-03-15 | 1999-12-07 | Amway Corporation | Discrete whitening agent particles method of making, and powder detergent containing same |
US6008174A (en) * | 1996-03-15 | 1999-12-28 | Amway Corporation | Powder detergent composition having improved solubility |
US6080711A (en) * | 1996-03-15 | 2000-06-27 | Amway Corporation | Powder detergent composition and method of making |
US6177397B1 (en) | 1997-03-10 | 2001-01-23 | Amway Corporation | Free-flowing agglomerated nonionic surfactant detergent composition and process for making same |
DE19882934B3 (de) * | 1997-12-30 | 2012-02-23 | Ecolab Inc. | Verbesserte alkalische Zusammensetzung in Form eines festen Blocks |
Also Published As
Publication number | Publication date |
---|---|
ATA859377A (de) | 1983-10-15 |
SE7713166L (sv) | 1978-06-03 |
NZ185756A (en) | 1979-12-11 |
AT374820B (de) | 1984-06-12 |
DK152588C (da) | 1988-09-05 |
IT1092161B (it) | 1985-07-06 |
PT67335B (en) | 1979-04-26 |
ES464644A1 (es) | 1978-12-16 |
GB1591517A (en) | 1981-06-24 |
ZA776947B (en) | 1979-10-31 |
CH633581A5 (de) | 1982-12-15 |
AU3095377A (en) | 1979-05-31 |
CA1096740A (en) | 1981-03-03 |
MY8300071A (en) | 1983-12-31 |
DK537077A (da) | 1978-06-03 |
FR2372892A1 (fr) | 1978-06-30 |
DK152588B (da) | 1988-03-21 |
DE2753026A1 (de) | 1978-06-08 |
PT67335A (en) | 1977-12-01 |
SE435729B (sv) | 1984-10-15 |
AU521529B2 (en) | 1982-04-08 |
NL7713386A (nl) | 1978-06-06 |
PH16878A (en) | 1984-04-02 |
FR2372892B1 (de) | 1982-11-05 |
BE861432A (fr) | 1978-03-31 |
DE2753026C2 (de) | 1990-04-19 |
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